Spectroscopic and DFT Characterization of a Highly Reactive Nonheme FeV -Oxo Intermediate

Journal of the American Chemical Society
Ruixi FanEckard Münck

Abstract

The reaction of [(PyNMe3)FeII(CF3SO3)2], 1, with excess peracetic acid at -40 °C generates a highly reactive intermediate, 2b(PAA), that has the fastest rate to date for oxidizing cyclohexane by a nonheme iron species. It exhibits an intense 490 nm chromophore associated with an S = 1/2 EPR signal having g-values at 2.07, 2.01, and 1.94. This species was shown to be in a fast equilibrium with a second S = 1/2 species, 2a(PAA), assigned to a low-spin acylperoxoiron(III) center. Unfortunately, contaminants accompanying the 2(PAA) samples prevented determination of the iron oxidation state by Mössbauer spectroscopy. Use of MeO-PyNMe3 (an electron-enriched version of PyNMe3) and cyclohexyl peroxycarboxylic acid as oxidant affords intermediate 3b(CPCA) with a Mössbauer isomer shift δ = -0.08 mm/s that indicates an iron(V) oxidation state. Analysis of the Mössbauer and EPR spectra, combined with DFT studies, demonstrates that the electronic ground state of 3b(CPCA) is best described as a quantum mechanical mixture of [(MeO-PyNMe3)FeV(O)(OC(O)R)]2+ (∼75%) with some FeIV(O)(•OC(O)R) and FeIII(OOC(O)R) character. DFT studies of 3b(CPCA) reveal that the unbound oxygen of the carboxylate ligand, O2, is only 2.04 Å away from the oxo group,...Continue Reading

References

Sep 13, 2002·Journal of the American Chemical Society·Arianna BassanLawrence Que
Mar 20, 2003·Proceedings of the National Academy of Sciences of the United States of America·Mi Hee LimLawrence Que
Dec 23, 2006·Science·Filipe Tiago de OliveiraTerrence J Collins
Mar 8, 2007·Journal of the American Chemical Society·Sarmistha ChakrabartyJohn D Lipscomb
Jun 5, 2007·Accounts of Chemical Research·Carsten KrebsJ Martin Bollinger
Dec 7, 2007·Journal of the American Chemical Society·Rubén Mas-Ballesté, Lawrence Que
Feb 19, 2008·Nature Chemical Biology·Elena G Kovaleva, John D Lipscomb
Aug 21, 2008·Journal of the American Chemical Society·Timothy A JacksonLawrence Que
Sep 23, 2009·Chemical Reviews·Paul R Ortiz de Montellano
Feb 22, 2011·Nature Chemistry·Marinus A BigiM Christina White
Mar 12, 2011·Accounts of Chemical Research·Christine E Tinberg, Stephen J Lippard
Mar 8, 2012·Nature Communications·Johannes HohenbergerKarsten Meyer
May 23, 2012·Journal of the American Chemical Society·Marinus A BigiM Christina White
Jul 13, 2012·Proceedings of the National Academy of Sciences of the United States of America·Katherine M Van HeuvelenLawrence Que
Nov 19, 2013·ACS Catalysis·Sarah M Barry, Gregory L Challis
Dec 3, 2013·Chemical Communications : Chem Comm·Olga V MakhlynetsElena V Rybak-Akimova
Jan 7, 2014·Journal of the American Chemical Society·Munmun GhoshSayam Sen Gupta
Sep 13, 2014·Journal of the American Chemical Society·Kallol RayWonwoo Nam
Nov 21, 2014·Chemistry : a European Journal·Soumen KunduTerrence J Collins
Feb 13, 2015·Journal of the American Chemical Society·Achintesh N BiswasLawrence Que
Jul 16, 2015·Accounts of Chemical Research·Mayank Puri, Lawrence Que
Jul 24, 2015·Accounts of Chemical Research·Wonwoo Nam
Oct 29, 2015·Chemical Society Reviews·Tim CernakShane W Krska
Nov 26, 2015·Journal of the American Chemical Society·Joan Serrano-PlanaMiquel Costas
Sep 1, 2016·Journal of the American Chemical Society·Sumit Sahu, David P Goldberg
Oct 11, 2016·Journal of the American Chemical Society·Matthew R MillsTerrence J Collins
Dec 3, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Xiongyi Huang, John T Groves
Jan 27, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Giorgio OlivoMiquel Costas
May 11, 2017·Chemical Reviews·Terrence J Collins, Alexander D Ryabov

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Citations

May 23, 2018·Angewandte Chemie·Verònica PostilsPedro Salvador
Apr 6, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Mainak MitraEbbe Nordlander
Mar 27, 2019·Chemistry : a European Journal·Santanu PattanayakSam P de Visser
May 6, 2020·Angewandte Chemie·Roman EzhovYulia Pushkar
Jul 23, 2018·Applied Microbiology and Biotechnology·Maciej SzaleniecMarina Donova
Feb 24, 2019·Nature Communications·Margarida BorrellMiquel Costas
Mar 4, 2021·Chemical Society Reviews·Xue-Peng ZhangWonwoo Nam
Aug 22, 2018·Inorganic Chemistry·Álvaro Martínez-CamarenaEnrique García-España
Mar 27, 2020·The Journal of Organic Chemistry·Akop YepremyanKayla N Green
Jul 19, 2019·The Journal of Physical Chemistry. a·Jian-Wei QinShu-Xian Hu
Jul 10, 2018·Journal of the American Chemical Society·Bhaskar MondalShengfa Ye
Sep 7, 2018·Journal of the American Chemical Society·M Christina White, Jinpeng Zhao
Sep 8, 2021·Inorganic Chemistry·Justin L LeeA S Borovik
Dec 18, 2021·Environmental Science & Technology·Virender K SharmaChing-Hua Huang

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